KR102132637B1 - Methods for processing oled devices - Google Patents

Abstract

A method of manufacturing an electronic device on a thin sheet (20) bonded to a carrier (10). The surface modification layer 30 and associated heat treatments control the sheet 20, carrier 10, to control both room temperature van der Waals (and/or hydrogen) bonding and hot covalent bonding between the thin sheet and carrier during electronic device processing. ), or both. Room temperature bonding is controlled to be sufficient to hold thin sheets and carriers together during vacuum processing, wet processing and/or ultrasonic cleaning processing, during electronic device processing. And at the same time, the high temperature covalent bonding is controlled to prevent permanent bonding between the thin sheet and the carrier during high temperature processing, during electronic device processing, as well as to maintain sufficient bonding to prevent peeling during high temperature processing.

Description

Processing method of OLED device {METHODS FOR PROCESSING OLED DEVICES}

This application claims priority to U.S. Application Serial No. 14/047514 filed on October 7, 2013 under 35 USC § 120, 35 U.S.C. Priority is claimed to U.S. Provisional Application Serial No. 61/736871 filed on December 13, 2012 under § 119, the contents of which are trusted and incorporated herein by reference in its entirety.

<Field of invention>

The present invention relates to articles and methods for processing electronic devices on flexible sheets on carriers, and more particularly articles and methods for processing electronic devices on flexible glass sheets on glass carriers.

Flexible substrates offer the promise of cheaper devices using roll-to-roll processing, and the potential to produce thinner, lighter, more flexible and more durable displays. However, the techniques, equipment, and methods necessary for roll-to-roll processing of high quality displays have not yet been fully developed. Since panel manufacturers have already invested heavily in a tool set for processing large sheets of glass, it is difficult to laminate flexible substrates into carriers and manufacture display devices by sheet-to-sheet processing. It provides a shorter solution to unfold the value proposition of a thinner, lighter, and more flexible display. The display was demonstrated in polymer sheets where the device fabrication was sheet to sheet with PEN laminated to a glass carrier, for example polyethylene naphthalate (PEN). The upper temperature limit of PEN limits the device quality and process that can be used. In addition, the high permeability of the polymer substrate results in environmental degradation of OLED devices requiring near-closed packages. Thin film encapsulation offers the potential to overcome these limitations, but it has not yet been demonstrated to provide acceptable yields at large doses.

In a similar manner, the display device can be manufactured using a glass carrier laminated to one or more thin glass substrates. It is expected that the low permeability of the thin glass and improved temperature and chemical resistance will enable a higher performance flexible display with higher performance.

However, thermal, vacuum, solvent and acidic, and ultrasonic, flat panel display (FPD) processes require strong bonding to thin glass bound to the carrier. FPD processes are typically vacuum deposition (sputtering metal, transparent conductive oxide and oxide semiconductors, chemical vapor deposition (CVD) deposition of amorphous silicon, silicon nitride, and silicon dioxide, and dry etching of metals and insulators), thermal processes (~300-400 ℃ CVD deposition, p-Si crystallization below 600°C, oxide semiconductor annealing at 350-450°C, dopant annealing at below 650°C, and contact annealing at ~200-350°C), acidic etching (metal etch, oxide semiconductor etch), solvent exposure (Deposition of stripping photoresist, polymer encapsulation), and ultrasonic exposure (for solvent stripping of photoresist and aqueous cleaning, typically in an alkaline solution).

Adhesive wafer bonding has been widely used in micromechanical systems (MEMS) and semiconductor processing for post-processing, where the process is less severe. Commercial adhesives by Brewer Science and Henkel are typically 5-200 micrometer thick, thick polymer adhesive layers. The wide thickness of these layers creates the possibility of contaminating large volumes of volatiles, trapped solvents, and adsorbed paper FPD processes. This material is thermally decomposed and releases gas above -250°C. The material can also cause contamination in downstream stages by acting as a sink for gases, solvents and acids that can outgas in subsequent processes.

In the United States Provisional Application Serial No. 61/596,727 (hereinafter referred to as US '727), filed on February 8, 2012, under the heading of processing flexible glass using a carrier, the concept therein is a thin sheet, for example, flexible The glass sheet is initially bonded to the carrier by the van der Waals force, and then the thin sheet/carrier is processed, thereby increasing the bond strength in a specific zone while maintaining the ability to remove a portion of the thin sheet, Disclosed includes forming a device (eg, an electronic or display device, a component of an electronic or display device, an organic light emitting device (OLED) material, a photo-power generation (PV) structure, or a thin film transistor). At least a portion of the thin glass is coupled to the carrier to prevent the device process fluid from entering between the thin sheet and the carrier, reducing the chance of contaminating downstream processes, ie, the combined seal between the thin sheet and the carrier is sealed , In some embodiments, this seal encloses the exterior of the article to prevent liquid or gas from intruding into or out of any region of the sealed article.

Further in US '727, low temperature polysilicon (LTPS) (lower temperature compared to solid phase crystallization processing which can be below about 750°C) device fabrication process, temperatures close to 600°C or higher, vacuum, and wet etch environments can be used Disclosed. These conditions limit the materials that can be used and place high demands on the carrier/thin sheet. Thus, what is required is the loss or contamination of the bond strength between the thin glass and the carrier at higher processing temperatures, using the manufacturer's existing capital infrastructure, and processing thin glass, i.e., glass having a thickness of less than 0.3 mm. It is a carrier approach that makes it possible without, and that thin glass is easily detached from the carrier at the end of the process.

One commercial advantage over the approach disclosed in US '727 is that, as mentioned in US '727, manufacturers can use thin glass sheets for PV, OLED, LCD and patterned thin film transistor (TFT) electronics, for example. The advantage is that they will be able to use their existing capital infrastructure for processing equipment. In addition, the approach includes a process for cleaning and surface preparation of thin glass sheets and carriers to promote bonding; A process for strengthening the bond between the thin sheet and the carrier in the joined region; A process for maintaining the peelability of the thin sheet from the carrier in the non-bonded (or reduced/low-strength bond) region; And a process for cutting thin sheets to facilitate tearing from the carrier.

In the glass-to-glass bonding process, the glass surface is cleaned to remove all metal, organic and particulate residues, leaving mainly silanol end surfaces. The glass surface is first brought into close contact, with van der Waals and/or hydrogen-bonding forces pulling the glass surface together. With heat and optionally pressure, the surface silanol groups condense to form strong covalent Si—O—Si bonds across the interface and permanently bond the glass fragments. Metal, organic and particulate residues will block the bond by shielding the surface to prevent tight contact required for bonding. The number of bonds per unit area will be determined by the likelihood that the two silanol species on opposite surfaces will react to condense and remove water, so a high silanol surface concentration is also required to form a strong bond. Zhuravlel reported the average number of hydroxyls per nm ² as 4.6 to 4.9 for well hydrated silica (Zhuravlel, LT, The Surface Chemistry of Amorphous Silika , Zhuravlev Model , Colloids and Surfaces A: Physiochemical Engineering Aspects 173 (2000) 1-38). In US '727, non-bonding zones are formed within the joined perimeter, and the primary method described for forming such non-bonding regions is to increase surface roughness. An average surface roughness Ra of more than 2 nm can prevent glass-to-glass bond formation during the elevated temperature bonding process. Controlled bonding under the heading of accelerated processing to control bonding between seats and carriers and in US Provisional Application Serial No. 61/736,880 (hereinafter US '880) filed on December 13, 2012 by the same inventor The region is formed by controlling van der Waals and/or hydrogen bonding between the carrier and the thin glass sheet, but covalent bonding regions are still used. Thus, articles and methods for processing thin sheets into carriers in US '727 and US '880 can withstand the harsh environment of FPD processing, but in some applications, reuse of carriers, covalently bonded, is undesirable. It is prevented by strong covalent bonds between the thin glass and the glass carrier in the zone, for example Si-O-Si bonds with ˜1000-2000 mJ/m 2 adhesion, similar to the breaking strength of glass. Frying or peeling cannot be used to separate the covalently bonded portion of the thin glass from the carrier, and thus the entire thin sheet cannot be removed from the carrier. Instead, areas that are not engaged with the device thereon are scribed or torn, leaving the bonded perimeter of the thin glass sheet on the carrier.

<Overview>

In view of the above, it is able to withstand the hardships of FPD processing, including high temperature processing (without emitting gases that would not match the semiconductor or display manufacturing process to be used), but thin sheets to allow reuse of carriers for processing of other thin sheets There is a need for a thin sheet-carrier article that allows the entire area of a product to be removed from the carrier (all at once, or divided). Described herein is a method of controlling the adhesion between the carrier and the thin sheet to cause a temporary bond that is strong enough to withstand FPD processing (including LTPS processing), but weak enough to allow detachment of the sheet from the carrier, even after high temperature processing. . Such controlled bonds can be used to create articles with reusable carriers, or alternatively articles with patterned regions of controlled and covalent bonds between the carrier and the sheet. More particularly, the present disclosure can be provided on thin sheets, carriers, or both, to control room temperature van der Waals, and/or both hydrogen bonds and hot covalent bonds, between thin sheets and carriers (various materials and Provides a surface modification layer (including associated surface heat treatment). Even more particularly, room temperature bonding can be controlled to be sufficient to hold thin sheets and carriers together during vacuum processing, wet processing and/or ultrasonic cleaning processing. And at the same time, the high temperature covalent bonding can be controlled to prevent permanent bonding between the thin sheet and the carrier during high temperature processing, as well as to maintain sufficient bonding to prevent peeling during high temperature processing. In an alternative embodiment, a surface modification layer is used to prepare for further processing options, such as maintaining the seal between the carrier and the sheet even after dicing the article into smaller pieces for further device processing. Along with the covalent bonding zones, it is possible to create a variety of controlled bonding zones, where the carrier and sheet remain sufficiently bonded throughout the various processes, including vacuum processing, wet processing and/or ultrasonic cleaning processing. Still further, some surface modification layers simultaneously reduce gas evolution emissions during harsh conditions in FPD (e.g. LTPS) processing environments, including high temperature and/or vacuum processing, while at the same time bonding between carrier and sheet Provides control.

Additional features and advantages will be described in the detailed description that follows, and in part will be readily apparent to those skilled in the art from the detailed description or may be learned by practicing various aspects as illustrated in the description and accompanying drawings. There will be. It should be understood that both the foregoing general description and the following detailed description are merely illustrative of various aspects and are intended to provide an overview or system for understanding the nature and features of the invention as claimed.

The accompanying drawings are included to provide a further understanding of the principles of the invention, and are incorporated into and constitute a part of this specification. The drawings serve to illustrate one or more embodiment(s) and, together with the detailed description, for example to illustrate the principles and operation of the invention. It should be understood that the various features disclosed in this specification and drawings can be used in any and all combinations. As a non-limiting example, various features can be combined with each other as described in the appended claims.

1 is a schematic side view of an article having a carrier bonded to a thin sheet comprising a surface modification layer therebetween.
FIG. 2 is a partial perspective and exploded assembly view of the article of FIG. 1;
3 is a graph of surface hydroxyl concentration for silica as a function of temperature.
4 is a graph of the surface energy of SC1-cleaned sheets of glass as a function of annealing temperature.
5 is a graph of the surface energy of a thin fluoropolymer film deposited on a sheet of glass as a function of the percentage of one of the constituent materials from which the film is made.
6 is a schematic top view of a thin sheet bonded to a carrier by bonding regions.
7 is a schematic diagram of a test setup.
8 is a collection of graphs of surface energy (of different parts of the test setup of FIG. A) for various materials under different conditions.
9 is a graph of changes in temperature versus% bubble area for various materials.
10 is another graph of changes in temperature versus% bubble area for various materials.

In the following detailed description, for purposes of explanation and not limitation, exemplary embodiments that disclose specific details are set forth to provide an overall understanding of the various principles of the invention. However, it will be apparent to those skilled in the art that, with the advantages of the present disclosure, the invention may be practiced in other embodiments that depart from the specific details disclosed herein. In addition, descriptions of well-known devices, methods and materials may be omitted so as not to obscure the description of various principles of the invention. Finally, whenever applied, the same reference numbers indicate the same components.

Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another embodiment includes from one particular value and/or to another particular value. Similarly, when a value is expressed as an approximation, by use of the preceding “about”, it will be understood that a particular value forms another embodiment. It will be further understood that the endpoints of each range are meaningful both with respect to the other endpoints and without regard to the other endpoints.

Directional terms as used herein-for example, up, down, right, left, front, back, top, bottom-are made only in connection with the drawings as shown and are not intended to indicate absolute directions.

As used herein, singular forms include plural subjects unless the context clearly dictates otherwise. Thus, for example, reference to a singular “component” includes aspects having two or more such components, unless the context clearly dictates otherwise.

In both US '727, and US '880, at least a portion of a thin glass sheet remains “unbonded” so that devices processed on the thin glass sheet can be removed from the carrier. A solution is provided that allows processing. However, the periphery of the thin glass is permanently (or covalently, or hermetically) bonded to the carrier glass through the formation of covalent Si—O—Si bonds. This covalently bonded periphery prevents the reuse of the carrier, as thin glass cannot be removed from this permanently bound zone without damaging the thin glass and carrier.

To maintain advantageous surface shape characteristics, the carrier is typically a display grade glass substrate. Thus, in some situations, simply disposing of the carrier after one use is wasteful and expensive. Therefore, to reduce the cost of display manufacturing, it is desirable if the carrier can be reused to process more than one thin sheet substrate. The present disclosure provides that thin sheets are subjected to high temperature processing, where high temperature processing is processing at a temperature of ≧400° C., and may vary depending on the type of device being manufactured, for example, amorphous silicon or amorphous indium gallium zinc oxide (IGZO) back plate. FPD processing lines, including temperatures below about 450°C, as in the case of processing, below about 500-550°C, as in the case of crystalline IGZO processing, or below about 600-650°C, as typical in LTPS processes Allows processing through harsh environments, yet allows thin sheets to be easily removed from the carrier without damage to the thin sheet or carrier (e.g., one of the carrier and the thin sheet breaks or cracks into two or more fragments) Thus, articles and methods are described that enable carriers to be reused.

1 and 2, the glass article 2 has a thickness 8, a carrier 10 having a thickness 18, a thin sheet 20 having a thickness 28 (ie, for example , 10-50 micrometer, 50-100 micrometer, 100-150 micrometer, 150-300 micrometer, 300, 250, 200, 190, 180, 170, 160, 150, 140, 130, 120, 110, 100 , Sheet having a thickness of ≤ 300 micrometers, including, but not limited to, thickness of 90, 80, 70, 60, 50, 40, 30, 20, or 10 micrometers), and having a thickness of 38 And a surface modification layer 30. The glass article 2 has a thin sheet 20 itself of ≤ 300 micrometers, but a thicker sheet (i.e. approximately ≥ .4 mm, e.g. .4 mm, .5 mm, .6 mm, .7 mm, .8 mm, .9 mm, or 1.0 mm sheet) is designed to allow processing of the thin sheet 20 in equipment designed for it. That is, the thickness (8), which is the sum of the thicknesses (18), (28), and (38), is processed by one piece of equipment, for example, equipment designed to place electronic device components on a substrate sheet. It is designed to be equivalent to the thickness of the thicker sheet that was designed. For example, if processing equipment is designed for a 700 micrometer sheet, and a thin sheet has a thickness 28 of 300 micrometers, then assuming that the thickness 18 is negligible, the thickness 38 is negligible. , 400 micrometers. That is, the surface modification layer 30 is not shown in a constant ratio; Instead, it is greatly exaggerated for illustrative purposes only. In addition, the surface modification layer is shown in perspective. Indeed, the surface modification layer will be uniformly disposed over the bonding surface 14 when providing a reusable carrier. Typically, the thickness 38 will be approximately nanometers, for example, 0.1 to 2.0, or 10 nm or less, and in some examples, 100 nm or less. The thickness 38 can be measured by an ellipsometer. In addition, the presence of the surface modification layer can be detected by surface chemistry analysis, for example ToF Sims mass spectrometry. Thus, the contribution of the thickness 38 to the article thickness 8 is negligible and for determining the thickness 18 of the carrier 10 suitable for processing a given thin sheet 20 having the thickness 28. It can be neglected in calculations. However, to the extent that the surface modification layer 30 has any significant thickness 38, such a design devises the thickness 18 of the carrier 10, a given thickness 28 of the thin sheet 20, and processing equipment. Can be considered in determining for a given thickness.

The carrier 10 has a first surface 12, a bonding surface 14, a periphery 16, and a thickness 18. Additionally, the carrier 10 can have any suitable material, including, for example, glass. The carrier need not be glass, but instead can be ceramic, glass-ceramic, or metal (since surface energy and/or bonding can be controlled in a manner similar to that described below with respect to the glass carrier). When made of glass, the carrier 10 can have any suitable composition including alumino-silicate, boro-silicate, alumino-boro-silicate, soda-lime-silicate, containing alkali or depending on its end use It may be alkali-free. The thickness 18 can be about 0.2 to 3 mm or more, for example 0.2, 0.3, 0.4, 0.5, 0.6, 0.65, 0.7, 1.0, 2.0, or 3 mm, or more, as mentioned above , Thickness 28, and thickness 38 if not negligible will depend on such. Further, the carrier 10 can be made of one layer, as shown, or of multiple layers joined together (including multiple thin sheets). In addition, the carrier is Gen 1 size or more, for example, Gen 2, Gen 3, Gen 4, Gen 5, Gen 8 or more (eg, sheet size 100 mm × 100 mm to 3 meters × 3 meters or more) Can have

The thin sheet 20 has a first surface 22, a bonding surface 24, a periphery 26, and a thickness 28. Peripherals 16 and 26 may have any suitable shape, may be identical to each other, or may be different from each other. In addition, the thin sheet 20 can have any suitable material, including, for example, glass, ceramic, or glass-ceramic. When made of glass, the thin sheet 20 can have any suitable composition, including alumino-silicate, boro-silicate, alumino-boro-silicate, soda-lime-silicate, and alkali depending on its end use It may be contained or alkali free. The thermal expansion coefficient of the thin sheet could be matched relatively close to the thermal expansion coefficient of the carrier to prevent warping of the article during processing at elevated temperatures. The thickness 28 of the thin sheet 20 is 300 micrometers or less, as mentioned above. In addition, the thin sheet may have a Gen 1 size or more, for example, Gen 2, Gen 3, Gen 4, Gen 5, Gen 8 or more (for example, a sheet size of 100 mm × 100 mm to 3 meters × 3 meters or more) ).

The article 2 will not only need to have the correct thickness processed in the existing equipment, but will also need to be able to withstand the harsh environment in which the processing takes place. For example, flat panel display (FPD) processing can include wet ultrasonic, vacuum, and high temperature (eg, ≧400° C.) processing. In some processes, as mentioned above, the temperature may be ≥ 500°C, or ≥ 600°C, and 650°C or less.

In order to withstand the harsh environment in which the article 2 will be processed, such as during FPD manufacturing, for example, the joining surface 14 is of sufficient strength so that the thin sheet 20 does not separate from the carrier 10. ). And this strength should be maintained throughout processing so that the thin sheet 20 does not separate from the carrier 10 during processing. In addition, in order to allow the thin sheet 20 to be removed from the carrier 10 (so that the carrier 10 can be reused), the bonding surface 14 can be formed by the originally designed bonding force, and/or For example, the article should not be too strongly bonded to the bonding surface 24 by the bonding force caused by a change in the originally designed bonding force that may occur when subjected to processing at a high temperature, for example, a temperature of ≥ 400°C. do. The surface modification layer 30 can be used to control the strength of the bond between the bond surface 14 and the bond surface 24 to achieve both of these purposes. The controlled bonding force is controlled by controlling the contribution of van der Waals (and/or hydrogen bonding) and shared attraction energy to the total adhesion energy controlled by adjusting the polar and non-polar surface energy components of the thin sheet 20 and carrier 10. Is achieved. This controlled bond withstands FPD processing (including wet, ultrasonic, vacuum, and thermal processes including processing temperatures of ≥ 400°C, and in some cases ≥ 500°C, or ≥ 600°C, and 650°C or less) It remains detachable by application of a sufficiently strong and sufficient separating force to the group and by force that will not cause catastrophic damage to the thin sheet 20 and/or carrier 10. Such desorption allows the removal of the thin sheet 20 and the devices fabricated thereon, and also allows reuse of the carrier 10.

Although the surface modification layer 30 is shown as a solid layer between the thin sheet 20 and the carrier 10, it need not be true. For example, layer 30 may be approximately 0.1 to 2 nm thick and cannot completely cover the integral portion of bonding surface 14. For example, the coverage may be ≦100%, 1% to 100%, 10% to 100%, 20% to 90%, or 50% to 90%. In other embodiments, layer 30 may be 10 nm thick or less, or in other embodiments 100 nm thick or less. The surface modification layer 30 can be considered to be disposed between the carrier 10 and the thin sheet 20 even though it cannot contact either the carrier 10 or the thin sheet 20. In any case, an important aspect of the surface modification layer 30 modifies the ability of the bonding surface 14 to bond with the bonding surface 24, thereby increasing the strength of bonding between the carrier 10 and the thin sheet 20. Control. The material and thickness of the surface modification layer 30, as well as the treatment of the bonding surfaces 14, 24 prior to bonding, can be used to control the strength of the bonding (adhesive energy) between the carrier 10 and the thin sheet 20. have.

In general, the adhesion energy between two surfaces is given by Equation 1 below ("A theory for the estimation of surface and interfacial energies. I. derivation and application to interfacial tension", LA Girifalco and RJ Good, J. Phys. Chem., V 61, p904):

<Equation 1>

In the above formula, γ ₁ , γ ₂ and γ ₁₂ are the surface energy of surface 1 and surface 2 and the interface energy of surface 1 and 2, respectively. Each surface energy usually has two terms; It is a combination of the dispersion component γ ^d and the polar component γ ^p :

<Equation 2>

When the adhesion was mainly due to the London dispersion force (γ ^d ) and polar force, for example hydrogen bonding (γ ^p ), the interfacial energy could be given by Equation 3 below (Girifalco and RJ Good)):

<Equation 3>

After substituting Equation 3 into Equation 1, the adhesive energy could be roughly calculated as follows:

<Equation 4>

In Equation 4 above, only van der Waals (and/or hydrogen bond) components of adhesion energy are considered. These include polar-polar interactions (Keesom), polar-non-polar interactions (Debye) and non-polar-non-polar interactions (London). However, other attraction energies, such as covalent and electrostatic bonds, may also be present. So, in a more generalized form, the equation is written as follows:

<Equation 5>

Where w _c and w _e are covalent and electrostatic adhesion energies. Covalent adhesion energy is rather common, as in silicon wafer bonding, in which the initial hydrogen bonded pair of wafers are heated to a higher temperature to convert many or all silanol-silanol hydrogen bonds to Si-O-Si covalent bonds. Initially, room temperature, hydrogen bonding produces an adhesion energy of approximately ~100-200 mJ/m 2 allowing separation of the bonded surface, while a fully covalently bonded wafer pair, such as that made during high temperature processing (approximately 400-800° C.), Has an adhesion energy of ˜1000-3000 mJ/m 2 that does not allow separation of the bonded surface; Instead, both wafers serve as monoliths. On the other hand, when the surface is completely coated with a surface energy material having both surfaces low enough to shield the effect of the underlying substrate, for example, using a fluoropolymer, the adhesion energy is the adhesion of the coating material. It will be energy, and is so low that it results in low or no adhesion between the bonding surfaces 14, 24, whereby the thin sheet 20 will not be able to be processed in the carrier 10. Two extreme cases are considered: (a) Standard clean 1 twice (SC1, as known in the art) Glass surfaces saturated with cleaned silanol groups are hydrogen bonded (the adhesion energy is ~100-200 mJ/ ㎡), and then bonded together at room temperature, and then heated to high temperature to convert the silanol group to a covalent Si-O-Si bond (the adhesion energy is 1000-3000 mJ/m 2 ). This latter adhesion energy is too high to be able to tear off a pair of glass surfaces; (b) The two glass surfaces fully coated with the fluoropolymer are bonded at room temperature with low surface adhesion energy (~12 mJ/m2 per surface) and heated to high temperature. In this latter case (b), not only the surface was not bound (because the total adhesion energy of ~24 mJ/m2 when the surfaces were combined is too low), but also the surface was not bonded at high temperatures due to the absence or too little of a polar reactive group. Does not. Between these two extremes, the range of adhesion energy exists, for example, between 50-1000 mJ/m 2, which can create a desired degree of controlled bonding. Therefore, the present inventors result in adhesion energy between these two extremes, and maintain a pair of glass substrates (e.g., glass carrier 10 and thin glass sheet 20) bonded to each other throughout the high seconds of FPD processing. Not only is it sufficient as necessary below, but also allows a controlled bond to be produced to the extent that it also permits the detachment of the thin sheet 20 from the carrier 10 after processing is completed (e.g. even after high temperature processing of ≧400° C.). Various methods have been found to provide the surface modification layer 30. In addition, the detachment of the thin sheet 20 from the carrier 10 is free of catastrophic damage to the carrier 10 by mechanical forces, and at least to no catastrophic damage to the thin sheet 20, so preferably also Can be done in such a way.

Equation (5) describes that the adhesion energy is a function of four surface energy parameters and, if any, covalent and electrostatic energy.

Proper adhesion energy can be achieved by careful selection of surface modifiers, ie surface modification layer 30, and/or heat treatment of the surface prior to bonding. Proper adhesion energy can be achieved by the selection of a chemical modifier of one or both of the bonding surface 14 and bonding surface 24, which in turn results in van der Waals (and/or hydrogen bonding, these terms are used throughout the specification). It is used to control both adhesion energy as well as similar covalent adhesion energy due to high temperature processing (eg, approximately ≧400° C.). For example, grabbing the bonding surface of SC1 cleaned glass (initially saturated with silanol groups with a high polar component of surface energy) and coating it with a low energy fluoropolymer, functional coating of the surface by polar and non-polar groups Provides rate control. This not only provides control of the initial Van der Waals (and/or hydrogen) bond at room temperature, but also provides control of the degree of covalent bond/covalent bond at higher temperatures. Control of the initial van der Waals (and/or hydrogen) bonds at room temperature allows one surface to another surface to allow vacuum and or rotary-rinse-dry (SRD) type processing, and in some cases also one easily formed surface Is performed to provide bonding to the other surface of the thin sheet 20 where the easily formed bonding is performed when squeezing the thin sheet 20 onto the carrier 10 using a squeegee or using a reduced pressure environment. It can be carried out at room temperature without the application of an externally applied force over the entire area of. That is, the initial Van der Waals bond provides at least the minimum degree of bonding that holds the thin sheets and carriers together so that they do not separate if one is retained and the other is capable of gravitational force. In most cases, the initial Van der Waals (and/or hydrogen) bonding will have such a degree that the article will also be able to undergo vacuum, SRD, and ultrasonic processing without peeling of the thin sheet from the carrier. Through both van der Waals (and/or hydrogen bonds) and covalent interactions through the surface modification layer 30 (including surface treatment of the material from which the surface modification layer is prepared and/or the surface to which the surface modification layer is applied), and/or Or this precise control to an appropriate level by heat treatment of the bonding surface before joining them together allows the thin sheet 20 to engage with the carrier 10 throughout the FPD style processing, while at the same time, after the FPD style processing The desired adhesion energy is achieved that allows the thin sheet 20 to be separated from the carrier 10 (by appropriate force to prevent damage to the thin sheet 20 and/or carrier). In addition, under appropriate circumstances, static charge could be applied to one or both glass surfaces to provide another level of control of the adhesion energy.

FPD processing, e.g., p-Si and oxide TFT fabrication, typically exceed 400° C., which will cause glass-to-glass bonding of the glass carrier 10 and the thin glass sheet 20 in the absence of the surface modification layer 30, 500 Thermal processes at temperatures above &lt;RTI ID=0.0&gt;C,&lt;/RTI&gt; Thus, control of the formation of Si-O-Si bonds results in reusable carriers. One way to control the formation of Si-O-Si bonds at elevated temperatures is to reduce the concentration of surface hydroxyls on the surfaces that can be bound.

Iler's plot of surface hydroxyl concentration on silica as a function of temperature (RK Iller: The Chemistry of Silica (Wiley-Interscience, New York, 1979)), The number of roxils (OH groups) decreases as the temperature of the surface increases, so heating of the silica surface (and, analogically, the glass surface, eg bonding surface 14 and/or bonding surface 24), By reducing the concentration of hydroxyls, the likelihood of hydroxyl interactions on the two glass surfaces is reduced, this reduction in surface hydroxyl concentration consequently reduces the Si-O-Si bonds formed per unit area, lowering the adhesion. However, removal of the surface hydroxyls requires a long annealing time at high temperatures (over 750° C. to completely remove the surface hydroxyls) Such long annealing times and high annealing temperatures are expensive processes, and strain points of typical display glass Exceeding the potential, resulting in an impractical process.

From the above analysis, the inventors have found that articles comprising thin sheets and carriers, suitable for FPD processing (including LTPS processing), can be produced by balancing the following three concepts:

(1) Modification of carrier and/or thin sheet bonding surface(s) by controlling initial room temperature bonding, which allows van der Waals (and/or hydrogen) bonding, enables initial room temperature bonding and non-high temperature FPD Produce medium adhesion energy (e.g., having a surface energy of >40 mJ/m 2 per surface prior to bonding surfaces) sufficient to withstand the process, e.g., vacuum processing, SRD processing, and/or ultrasonic processing. Control;

(2) in a thermally stable manner to withstand the FPD process without gas release which may cause undesired contamination in the fabrication process of semiconductors and/or displays in which the article may be used and/or unacceptable contamination in device fabrication. Surface modification of carriers and/or thin sheets of; And

(3) Control of binding at high temperature, this can be done by controlling the carrier surface hydroxyl concentration, and the concentration of other species capable of forming strong covalent bonds at elevated temperatures (eg, ≥ 400°C temperature), This ensures that the adhesive force between the carrier and the thin sheet at least does not damage the thin sheet (and preferably does not damage the thin sheet or carrier) even after high temperature processing (especially during the thermal process in the 500-650°C range, such as in the FPD process). ), the bonding energy between the bonding surface of the carrier and the thin sheet is such that the carrier and the thin sheet are within a range that allows detachment of the thin sheet from the carrier with sufficient separation force to maintain the bond between them so as not to peel during processing. Can be controlled.

In addition, we allow the use of the surface modification layer 30 to be controlled in a FPD type process (including vacuum and wet processes), such as controlled bond regions, ie article 2, with appropriate bonding surface preparation. Provides room temperature bonding between the thin sheet 20 and the carrier 10 sufficient for the following, but the thin sheet 20 is the carrier after the article 2 finishes high temperature processing, for example, FPD type processing, or LTPS processing. The covalent bond between the thin sheet 20 and the carrier 10 (even at elevated temperatures of ≥ 400° C.) can be removed from (10) (without damage to the thin sheet, and preferably also without damage to the carrier). It has been found that it can be balanced with the above concept to easily achieve a controlled bonding region. Each suitability was evaluated using a series of tests to evaluate possible bond surface preparation, and surface modification layers that would provide a reusable carrier suitable for FPD processing. Different FPD applications have different requirements, but the LTPS and oxide TFT processes appear to be the most stringent at this point, and therefore, the tests representative of the steps in these processes were chosen because they are the applications required for article (2). Vacuum processes, wet cleaning (including SRD and ultrasonic type processes) and wet etching are common to many FPD applications. Typical aSi TFT fabrication requires processing below 320°C. Annealing at 400°C is used in oxide TFT processes, while crystallization and dopant activation steps above 600°C are used in LTPS processing. Thus, the following five tests were used to enable a specific bonding surface preparation and surface modification layer 30 to allow the thin sheet 20 to remain bound to the carrier 10 throughout the FPD processing, while such processing (≥ 400 The possibility of allowing the thin sheet 20 to be removed from the carrier 10 (without damaging the thin sheet 20 and/or the carrier 10) after processing at a temperature of ℃) was evaluated. The tests were performed in sequence and samples were run from one test to the next unless there was a type of failure that would not allow subsequent testing.

(1) Vacuum test. The vacuum compatibility test was performed on an STS Multiplex PECVD load lock (available from SPTS, Newport, UK)-Load Lock is an Ebara A10S dry pump with soft pump valve (Ebara, Sacramento, Calif.) Pumped by Technologies Inc. (available from Ebara Technologies Inc.). The sample was placed in a loadlock, and then the loadlock was punctured from atmospheric pressure to 70 mTorr in 45 seconds. The failure, indicated by the notation “F” in the “Vacuum” column of the table below, was considered to have occurred when: (a) Loss of adhesion between the carrier and the thin sheet (by visual inspection using the naked eye, Failure here was considered to have occurred if the thin sheet had fallen off the carrier or was partially detached from it); (b) Bubbling between the carrier and the thin sheet (as determined by visual inspection using the naked eye-photographs of the samples were taken before and after processing, then compared, and the failure occurred when the defect increased in size by the dimensions visible to the naked eye. Decision); Or (c) movement of the thin sheet relative to the carrier (as determined by visual inspection using the naked eye-a picture of the sample was taken before and after the test, where the failure was the movement of binding defects, eg, in the presence of bubbles, or It was deemed to have occurred if the edges were detached, or if there was movement of a thin sheet in the carrier). In the table below, the notation “P” in the “Vacuum” column indicates that the sample did not fail according to the above criteria.

(2) Wet process test. Wet process compatibility testing was conducted using a Semitool model SRD-470S (available from Applied Materials, Santa Clara, Calif.). The test consisted of rinsing at 500 rpm for 60 seconds, Q-rinse at 15 MOhm-cm at 500 rpm, purging 10 seconds at 500 rpm, drying 90 seconds at 1800 rpm, and drying 180 seconds at 2400 rpm under running warm nitrogen. The failure, as indicated by the notation “F” in the “SRD” column of the table below, was considered to have occurred when: (a) Loss of adhesion between the carrier and the thin sheet (for visual inspection using the naked eye) By, the failure here was considered to have occurred if the thin sheet had fallen off the carrier or was partially detached from it); (b) Bubbling between the carrier and the thin sheet (as determined by visual inspection using the naked eye-photographs of the samples were taken before and after processing, then compared, and the failure occurred when the defect increased in size by the dimensions visible to the naked eye. Decision); Or (c) movement of the thin sheet relative to the carrier (as determined by visual inspection using the naked eye-a picture of the sample was taken before and after the test, where the failure was the movement of binding defects, eg, in the presence of bubbles, or Deemed to have occurred if the edges were detached, or if there was movement of a thin sheet in the carrier); Or (d) penetration of water under a thin sheet (as determined by visual inspection with an optical microscope at 50x magnification, where failure was determined to have occurred if liquid or residue could be observed). In the table below, the notation “P” in the “SRD” column indicates that the sample did not fail according to the above criteria.

(3) Temperature test up to 400°C. The 400° C. process compatibility test was performed using Alwin21 Accuthermo610 RTP (available from Alwin21, Santa Clara, Calif.). The carrier comprising the thin sheet bound to the carrier was circulated from room temperature to 400°C at 6.2°C/min, held at 400°C for 600 seconds, and heated in a chamber cooled to 300°C at 1°C/min. The carrier and thin sheet could then be cooled to room temperature. The failure, as indicated by the notation “F” in the “400° C.” column of the table below, was considered to have occurred when: (a) loss of adhesion between the carrier and the thin sheet (visual appearance inspection By, the failure here was considered to have occurred if the thin sheet fell from the carrier or was partially detached from it); (b) Bubbling between the carrier and the thin sheet (as determined by visual inspection using the naked eye-photographs of the samples were taken before and after processing, then compared, and the failure occurred when the defect increased in size by the dimensions visible to the naked eye. Decision); Or (c) increased adhesion between the carrier and the thin sheet (such increased adhesion (by insertion of a razor blade between the thin sheet and the carrier, and/or 2-3" thin glass of 100 square mm (New York Dessert Material 쌩 Damage to thin sheets or carriers by attaching a Kapton™ tape, 1" wide x 6" long piece to a thin sheet and pulling the tape) to adhere to a Govin Performance Plastic (K102 series from Saint Gobain Performance Plastic) Without removing the thin sheet from the carrier, wherein the failure is when there is damage to the thin sheet or carrier when an attempt is made to separate the thin sheet or carrier, or the thin sheet and carrier are subjected to the performance of any of the above detachment methods. It was considered to have occurred when it could not be desorbed by the desorption. It was determined to allow the removal of the thin sheet from the carrier prior to temperature cycling In the table below, the notation “P” in the “400° C.” column indicates that the sample did not fail according to the above criteria.

(4) Temperature test up to 600°C. The 600°C process compatibility test was performed using Alwin21 Accuthermo610 RTP. The carrier comprising the thin sheet was circulated from room temperature to 600° C. at 9.5° C./min, held at 600° C. for 600 seconds, and then heated in a chamber cooled to 300° C. at 1° C./min. The carrier and thin sheet could then be cooled to room temperature. The failure, as indicated by the notation “F” in the “600° C.” column of the table below, was considered to have occurred when: (a) Loss of adhesion between the carrier and the thin sheet (visual appearance inspection By, the failure here was considered to have occurred if the thin sheet fell from the carrier or was partially detached from it); (b) Bubbling between the carrier and the thin sheet (as determined by visual inspection using the naked eye-photographs of the samples were taken before and after processing, then compared, and the failure occurred when the defect increased in size by the dimensions visible to the naked eye. Decision); Or (c) increased adhesion between the carrier and the thin sheet (such increased adhesion (by inserting a razor blade between the thin sheet and the carrier, and/or attaching a piece of Kapton™ tape as described above to the thin sheet and applying the tape) Prevents the detachment of the thin sheet from the carrier without damaging the thin sheet or carrier, where the failure is if there is damage to the thin sheet or carrier when attempting to separate the thin sheet or carrier, or the thin sheet and carrier Was considered to have occurred if it could not be detached by performing any of the above desorption methods). Also, after bonding the thin sheet with the carrier and before thermal cycling, a desorption test is performed on the representative sample to determine that certain materials, and any associated surface treatments, allow the detachment of the thin sheet from the carrier prior to temperature cycling. did. In the table below, the notation “P” in the “600° C.” column indicates that the sample did not fail according to the above criteria.

(5) Ultrasound test. The ultrasonic compatibility test was performed by washing the articles in four tank lines, and the articles were processed from tank #1 to tank #4 sequentially in each tank. The tank dimensions for each of the four tanks were 18.4"L x 10"W x 15"D. The two cleaning tanks (#1 and #2) were in Yokohama, Japan, Oil & Pats Industries, Yokohama, Japan in deionized water at 50°C. Contains 1% Semiclean KG, available from Company Limited (Yokohama Oils and Fats Industry Co Ltd.) Cleaning Tank #1 is a NEY Prosonic 2 104 kHz ultrasonic generator (Blackstone, Janestown, NY) )-NEY Ultrasonic), and Wash Tank #2 was stirred with a NEY Prosonic 2 104 kHz ultrasonic generator Two rinse tanks (Tank #3 and Tank #4) contained deionized water at 50°C. Rinse tank #3 was stirred with a NEY sweepsonic 2D 72 kHz ultrasonic generator and rinse tank #4 was stirred with a NEY sweepsonic 2D 104 kHz ultrasonic generator, the process was performed for 10 minutes in each tank #1-4. The sample was then removed from tank #4 followed by rotary rinse drying (SRD) The failure, as indicated by the notation “F” in the “Ultrasonic” column of the table below, occurred when the following were present: It was considered: (a) loss of adhesion between the carrier and the thin sheet (by visual inspection with the naked eye, failure here was deemed to have occurred if the thin sheet fell from the carrier or partially detached from it); (b) the carrier And bubbling between thin sheets (as determined by visual inspection using the naked eye-samples of the samples were taken before and after processing, then compared, and the failure was determined to occur when the defect increased in size by the visible dimensions) Or (c) the formation of other significant defects (as determined by visual inspection with an optical microscope at 50x magnification, where failure is considered to have occurred if there were particles bound between the thin sheet and carrier that were not previously observed Lost); Or (d) penetration of water under a thin sheet (as determined by visual inspection with an optical microscope at 50x magnification, where failure was determined to have occurred if liquid or residue could be observed). In the table below, the notation “P” in the “Ultrasonic” column indicates that the sample did not fail according to the above criteria. In addition, in the table below, blanks in the "ultrasound" column indicate that the samples were not tested in this way.

Preparation of bonding surfaces subjected to hydroxyl reduction by heating

The advantage of modifying one or more of the bonding surfaces 14, 24 with the surface modification layer 30 so that the article 2 can successfully undergo FPD processing (i.e., the thin sheet 20 is attached to the carrier 10 during processing). The article (2, which remains bonded but can be separated from the carrier 10 after processing, including high temperature processing), has a glass carrier 10 and a thin glass sheet 20 without a surface modification layer 30 therebetween. ). In particular, attempts were made to prepare the bonding surfaces 14, 24 by first heating to reduce hydroxyl groups, but without the surface modification layer 30. The carrier 10 and the thin sheet 20 were cleaned, the bonding surfaces 14 and 24 were bonded to each other, and then the article 2 was tested. A typical cleaning process for preparing a binding glass is dilute hydrogen peroxide and base in which the glass is diluted (usually ammonium hydroxide, but a tetramethylammonium hydroxide solution such as JT Baker JTB-100 or JTB-111 can also be used) It is the SC1 cleaning process to be washed in. Cleaning removes particles from the bonding surface and creates a known surface energy, ie, it provides a reference for surface energy. Other types of cleaning may be used as the type of cleaning need not be SC1, and the type of cleaning will only have a very small effect on the silanol groups on the surface. The results of the various tests are described in Table 1 below.

Strong but separable initial, room temperature or van der Waals and/or hydrogen-bonded, approximately 0.2 nm, each available from Eagle XG® Display Glass (Corning Incorporated, Corning, NY) A thin glass sheet of 100 square mm×100 micrometer thick, including alkali-free, alumino-boro-silicate glass) with an average surface roughness Ra of 0.50 or 150 mm diameter single average flat (SMF) wafer or It was caused by simply cleaning the 0.63 mm thick glass carrier. In this example, the glass was washed for 10 minutes in a 65° C. bath of 40:1:2 deionized water: JTB-111: hydrogen peroxide. The thin glass or glass carrier may or may not have been annealed in nitrogen at 400° C. for 10 minutes to remove residual water—notation of “400° C.” in the “carrier” column or “thin glass” column of Table 1 below It shows that the sample was annealed in nitrogen at 400° C. for 10 minutes. FPD process suitability testing demonstrates that this SC1-SC1 initial, room temperature, bond is mechanically strong enough to pass vacuum, SRD and ultrasonic tests. However, heating at 400° C. and above caused a permanent bond between the thin glass and the carrier, ie, the thin glass sheet could not be removed from the carrier without damaging either or both of the thin glass sheet and the carrier. And this was also true for Example 1c, where each carrier and thin glass had an annealing step to reduce the concentration of surface hydroxyls. Thus, the above-described preparation of the bonding surfaces 14, 24 that have undergone only heating and then the bonding of the carrier 10 and the thin sheet 12 without the surface modification layer 30, the FPD process with a temperature of ≥ 400°C It is not a controlled bond suitable for.

Preparation of bonding surfaces by hydroxyl reduction and surface modification layer

Hydroxyl reduction, such as by heat treatment, and the surface modification layer 30 can be used together to control the interaction of the bonding surfaces 14, 24. For example, the binding energy of the bonding surfaces 14, 24 (both van der Waals and/or hydrogen-bonding at room temperature due to polar/dispersive energy components, and covalent bonding at high temperatures due to covalent energy components) is , Can be controlled to provide varying bonding strengths from difficult to room temperature bonding to allowing easy room temperature bonding and separation of bonding surfaces after high temperature processing,-after high temperature processing-to prevent the surface from separating without damage. . In some applications (as described in the thin sheet/carrier concept of US '727, and as described below), as in the case where the surface is in the "non-bonding" zone, It may be desirable to have no bonds, or very weak bonds. In other applications, for example, providing a reusable carrier for FPD processes, etc., where process temperatures of ≥ 500° C., or ≥ 600° C., and 650° C. or less can be achieved. And have sufficient van der Waals and/or hydrogen-bonds to put the carriers together, but it is desirable to prevent or limit high temperature covalent bonds. In another application, as described in the thin sheet/carrier concept of US '727, and as discussed below, (as discussed below), as in the case where the surface is in the "bonding zone", It may be desirable to have room temperature bonds sufficient to put the thin sheet and carrier together, and also develop strong covalent bonds at high temperatures. While not wishing to be bound by theory, in some cases a surface modification layer can be used to control room temperature bonding where thin sheets and carriers are initially bonded together, while (by surface heating, or, for example, surface modification Reduction of hydroxyl groups at the surface) (such as by reaction of a layer with hydroxyl groups) can be used to control covalent bonding, particularly covalent bonding at high temperatures.

The material for the surface modification layer 30 includes energy on the bonding surfaces 14, 24 (eg, energy of <40 mJ/m 2, as measured for one surface, and polarity and dispersion components) And the surface only creates weak bonds. In one embodiment, hexamethyldisilazane (HMDS) can be used to induce this low energy surface by reacting with surface hydroxyls, leaving a trimethylsilyl (TMS) end surface. HMDS can be used together as a surface modification layer while heating the surface to reduce hydroxyl concentration to control both room temperature and hot bonding. By selecting a suitable bonding surface preparation for each bonding surface 14, 24, an article having various abilities can be achieved. More particularly, among the interesting in providing reusable carriers for LTPS processing, the respective vacuum SRD, 400° C. (parts a and c), and 600° C. (parts a and c), to withstand (or pass) processing tests. ) A suitable bond can be achieved between the thin glass sheet 20 and the glass carrier 10.

In one embodiment, HMDS treatment of both the thin glass and carrier after SC1 cleaning results in a weakly bound surface that challenges bonding at room temperature with van der Waals (and/or hydrogen bonding) forces. Mechanical force is applied to bond the thin glass to the carrier. As shown in Example 2a of Table 2, this bond is weak enough, carrier warpage was observed in vacuum testing and SRD processing, bubbling (perhaps due to gas evolution) was observed in the 400°C and 600°C thermal processes, Particulate defects were observed after sonication.

In another embodiment, HMDS treatment of only one surface (carrier in the cited example) results in stronger room temperature adhesion to withstand vacuum and SRD processing. However, the thermal process at 400° C. and above permanently bound the thin glass to the carrier. It is calculated that the maximum surface coverage of trimethylsilyl groups on silica is 2.8/nm ² by Sindorf and Maciel in J. Phys. Chem. 1982, 86, 5208-5219. And in the Journal of Non-Crystalline Solids 316 (2003) 349-363, compared to a hydroxyl concentration of 4.6-4.9/nm ^{2 for} a fully hydroxylated silica by Suratwala et al., 2.7/ As measured as nm ² , this is not unexpected. That is, the trimethylsilyl group binds to some surface hydroxyls, but some unbound hydroxyls will remain. Thus, condensation of surface silanol groups would be expected to permanently bond the thin glass and carrier at a given sufficient time and temperature.

Various surface energies can be caused by heating the glass surface to reduce the surface hydroxyl concentration prior to HMDS exposure, resulting in an increased polar component of the surface energy. This not only reduces the driving force for the formation of covalent Si—O—Si bonds at high temperatures, but also results in stronger room temperature bonds, for example van der Waals (and/or hydrogen) bonds. 4 shows the surface energy of the Eagle XG® display glass carrier after annealing and after HMDS treatment. The increased annealing temperature before HMDS exposure increases the polar contribution (line 404), thereby increasing the total (polar and dispersion) surface energy (line 402) after HMDS exposure. It is also seen that the dispersion contribution to total surface energy (line 406) remains largely unchanged by heat treatment. While not wishing to be bound by theory, the increase in polarity components on the surface after HMDS treatment, and thereby the increase in total energy, is due to the fact that there is some exposed glass surface area even after HMDS treatment due to the sub-monolayer TMS coverage by HMDS. It seems to be attributed.

In Example 2b, a thin glass sheet was heated under vacuum at a temperature of 150° C. for one hour before binding to a non-heat-treated carrier with a coating of HMDS. This heat treatment of the thin glass sheet was not sufficient to prevent permanent bonding of the thin glass sheet to the carrier at a temperature of ≥ 400°C.

As shown in Example 2c-2e of Table 2, varying the annealing temperature of the glass surface prior to HMDS exposure can change the binding energy of the glass surface to control the bond between the glass carrier and the thin glass sheet.

In Example 2c, the carrier was annealed under vacuum at a temperature of 190° C. for 1 hour, followed by HMDS exposure to provide a surface modification layer 30. In addition, the thin glass sheet was annealed under vacuum at 450° C. for 1 hour before bonding with the carrier. The resulting article survived vacuum, SRD, and 400° C. tests (parts a and c, but with increased bubbling, so it failed to pass part b), but failed the 600° C. test. Thus, there was an increased resistance to hot bonds compared to Example 2b, but this was not sufficient to produce an article for processing at a temperature where the carrier is reusable> 600° C. (eg LTPS processing).

In Example 2d, the carrier was annealed under vacuum at a temperature of 340° C. for 1 hour, followed by HMDS exposure to provide a surface modification layer 30. Once more, the thin glass sheet was annealed under vacuum at 450° C. for 1 hour before bonding with the carrier. The results were similar to the results of Example 2c, and the article survived vacuum, SRD, and 400°C tests (parts a and c, but there was increased bubbling and did not pass part b), but failed the 600°C test. .

As shown in Example 2e, after annealing both the thin glass and the carrier under vacuum at 450° C. for 1 hr, HMDS exposure of the carrier was performed, followed by bonding the carrier and the thin glass sheet, for permanent bonding. Increase temperature resistance. Annealing the two surfaces to 450° C. prevents permanent binding after RTP annealing at 600° C. for 10 minutes, ie, this sample did not pass part b due to 600° C. processing tests (parts a and c, but increased bubbling; Similar results were observed for the 400°C test).

In Examples 2a-2e above, each carrier and thin sheet was Eagle XG® glass, where the carrier was a 150 mm diameter SMF wafer 630 micrometers thick and the thin sheet was 100 square mm 100 micrometers thick. HMDS was applied by pulse deposition in an YES-5 HMDS oven (available from Yield Engineering Systems, San Jose, Calif.), and the surface coverage may be less than one monolayer, ie, part of the surface hydroxyl Is not covered by HMDS as mentioned by Masiel and discussed above, but HMDS was one atomic layer thick (ie about 0.2 to 1 nm). Due to the small thickness in the surface modification layer, there is less risk of gas evolution which can lead to contamination during device fabrication. Also, as indicated in Table 2 by the "SC1" notation, each carrier and thin sheet was cleaned using the SC1 process prior to heat treatment or any subsequent HMDS treatment.

The comparison of Example 2b and Example 2a shows that the binding energy between the thin sheet and the carrier can be controlled by varying the number of surfaces comprising the surface modification layer. In addition, the bonding force between the two bonding surfaces can be controlled by controlling the bonding energy. In addition, a comparison of Examples 2b-2e shows that the bonding energy of the surface can be controlled by varying the parameters of the heat treatment applied to the bonding surface prior to application of the surface modifying material. Once more, heat treatment can be used to reduce the number of surface hydroxyls, thus controlling the degree of covalent bonding, especially at high temperatures.

Other materials, which can act in different ways to control the surface energy at the bonding surface, can be used for the surface modification layer 30 to control room temperature and hot bonding between the two surfaces. For example, one or two bonding surfaces are modified with a surface modification layer that coats or sterically blocks species, for example hydroxyl, to prevent the formation of strong permanent covalent bonds between the carrier and the thin sheet at elevated temperatures. Reusable carriers can also be created when producing. One way to generate adjustable surface energy and to coat the surface hydroxyls to prevent the formation of covalent bonds is the deposition of plasma polymer films, such as fluoropolymer films. Plasma polymerization can be at atmospheric pressure or reduced pressure and a source gas, such as a fluorocarbon source (including CF4, CHF3, C2F6, C3F6, C2F2, CH3F, C4F8, chlorofluorocarbon, or hydrochlorofluorocarbon), hydrocarbons, e.g. Plasma from, for example, alkanes (including methane, ethane, propane, butane), alkenes (including ethylene, propylene), alkynes (including acetylene), and aromatics (including benzene, toluene), hydrogen, and other gas sources, such as SF6 A thin polymer film is deposited under excitation (DC or RF parallel plate, inductively coupled plasma (ICP) electron cyclotron resonance (ECR) downstream microwave or RF plasma). Plasma polymerization creates a layer of highly crosslinked material. Control of reaction conditions and source gas can be used to control film thickness, density, and chemical properties to tailor the functional groups to the desired application.

5 is a total of plasma polymerized fluoropolymer (PPFP) films deposited from CF4-C4F8 mixture using Oxford ICP380 etch tool (available from Oxford Instruments, Oxfordshire, UK) (line 502) ) Surface energy (including polar (line 504) and dispersion (line 506) components). The film was deposited on a sheet of Eagle XG® glass, and spectroscopic elliptical polarization showed that the film was 1-10 nm thick. As can be seen from Figure 5, the glass carrier treated with a plasma polymerized fluoropolymer film containing less than 40% C4F8 exhibits >40 mJ/m 2 surface energy and thin glass by van der Waals or hydrogen bonding at room temperature and It creates a controlled bond between carriers. Accelerated bonding is observed when initially binding the carrier and thin glass at room temperature. That is, if a thin sheet is placed on the carrier and they are pressed together at one point, the wave front moves across the carrier, but at a slower rate than observed for SC1 treated surfaces without a surface modification layer thereon. do. Controlled bonding is sufficient to withstand all standard FPD processes including vacuum, wet, ultrasonic, and thermal processes below 600°C, i.e., this controlled bonding allows for 600°C processing testing without the movement or peeling of thin glass from the carrier. Passed. Desorption was accomplished by peeling with a razor blade and/or Kapton™ tape as described above. The process suitability of two different PPFP films (deposited as described above) is shown in Table 3. PPFP 1 of Example 3a was formed with C4F8/(C4F8+CF4)=0, that is, formed with CF4/H2 rather than C4F8, and PPFP 2 of Example 3b was deposited with C4F8/(C4F8+CF4)=0.38. Became. Both types of PPFP films survived vacuum, SRD, 400°C and 600°C processing tests. However, peeling was observed showing insufficient adhesion to withstand such processing after 20 minutes of ultrasonic cleaning of PPFP 2. Nevertheless, the surface modification layer of PPFP2 may be useful for some applications, such as when ultrasonic processing is not required.

In Examples 3a and 3b above, each carrier and thin sheet were Eagle XG® glass, where the carrier was a 150 mm diameter SMF wafer 630 micrometer thick and the thin sheet was 100 square mm 100 micrometer thick. Due to the small thickness in the surface modification layer, there is less risk of gas evolution which can lead to contamination during device fabrication. Also, the risk of outgassing is less because the surface modification layer did not appear to decompose once more. In addition, as shown in Table 3, each thin sheet was cleaned using the SC1 process before heat treatment under vacuum for 1 hour at 150°C.

Another material, which can act in different ways to control surface energy, can be used as a surface modification layer to control room temperature and high temperature bonding between thin sheets and carriers. For example, a bonding surface that can produce a controlled bond can be caused by silane treatment of a glass carrier and/or a thin sheet of glass. Silane is selected to produce suitable surface energy and to have sufficient thermal stability for the application. Silane that reacts with surface silanol groups by cleaning the carrier or thin glass that can be treated by a process, such as O2 plasma or UV-ozone, and SC1 or standard clean toe (SC2, as known in the art) cleaning It can remove organic substances and other impurities (eg, metals) that will interfere with. Other chemical based washings, such as HF, or H2SO4 washing chemicals, may also be used. The carrier or thin glass can be heated to control the surface hydroxyl concentration prior to silane application (as discussed above with respect to the surface modification layer of HMDS), and/or complete silane condensation with the surface hydroxyl after application of the silane Can be heated. The concentration of unreacted hydroxyl groups after silanation can be made low enough prior to bonding to prevent permanent bonding between the thin glass and the carrier at a temperature of ≧400° C., ie to form a controlled bond. This approach is described below.

Example 4a

The condensation was completed by treating the O2 plasma and SC1 treated glass carriers with 1% dodecyltriethoxysilane (DDTS) in toluene and annealing at 150° C. under vacuum for 1 hr. The DDTS treated surface showed a surface energy of 45 mJ/m 2. As shown in Table 4, a thin sheet of glass (SC1 cleaned and heated for 1 hour under vacuum at 400° C.) was bonded to the carrier binding surface with a DDTS surface modification layer on top. The article withstands wet and vacuum process tests, but due to the thermal decomposition of the silane, it could not withstand thermal processes above 400° C. without bubble formation under the carrier. This thermal decomposition is all linear alkoxy and chloro alkylsilanes R1 _x Si(OR2) _y (Cl) _z (where x=1 to 3, and y+z=4-x, methyl to produce a coating with good thermal stability, It is expected in the case of dimethyl, and trimethyl silane (x=1 to 3, R1=CH ₃ ).

Example 4b

The glass carrier treated with the O2 plasma and SC1 treated surface was then treated with 1% 3,3,3, trifluoropropyltriethoxysilane (TFTS) in toluene and annealed under vacuum at 150° C. for 1 hr to condense. Done. The TFTS treated surface showed a surface energy of 47 mJ/m 2. As shown in Table 4, a thin sheet of glass (SC1 cleaned and then heated under vacuum at 400° C. for 1 hour) was bonded to a carrier bonding surface with a TFTS surface modification layer on top. This article survived vacuum, SRD, and 400°C process tests without permanent bonding of the glass thin sheet to the glass carrier. However, the 600° C. test resulted in bubble formation under the carrier due to thermal decomposition of the silane. This was not unexpected because of the limited thermal stability of the propyl group. Although this sample failed the 600°C test due to bubbling, the material and heat treatment of this sample can be used in some applications where bubbles and their side effects, such as a decrease in surface flatness, or increased surface wave form can be tolerated. .

Example 4c

The glass carrier treated with O2 plasma and SC1 with a bonding surface was then treated with 1% phenyltriethoxysilane (PTS) in toluene and annealed at 200° C. under vacuum for 1 hr to complete condensation. The PTS treated surface showed a surface energy of 54 mJ/m 2. As shown in Table 4, a thin sheet of glass (SC1 washed and then heated under vacuum at 400° C. for 1 hour) was bonded to a carrier binding surface with a PTS surface modification layer. This article survived vacuum, SRD, and thermal processes below 600°C without permanent bonding of the glass carrier and the glass thin sheet.

Example 4d

The glass carrier treated with O2 plasma and SC1 with a bonding surface was then treated with 1% diphenyldiethoxysilane (DPDS) in toluene and annealed at 200° C. under vacuum for 1 hr to complete condensation. The DPDS treated surface exhibited a surface energy of 47 mJ/m 2. As shown in Table 4, a thin sheet of glass (SC1 washed and then heated under vacuum at 400° C. for 1 hour) was bonded to a carrier binding surface with a DPDS surface modification layer. This article survived vacuum and SRD tests, as well as thermal processes below 600°C, without permanent bonding of the glass carrier and glass thin sheet.

Example 4e

The glass carrier treated with the O2 plasma and SC1 treated surface was then treated with 1% 4-pentafluorophenyltriethoxysilane (PFPTS) in toluene and annealed at 200° C. under vacuum for 1 hr to complete condensation. The PFPTS treated surface showed a surface energy of 57 mJ/m 2. As shown in Table 4, a thin sheet of glass (SC1 washed and then heated under vacuum at 400° C. for 1 hour) was bonded to a carrier binding surface with a PFPTS surface modification layer. This article survived vacuum and SRD tests, as well as thermal processes below 600°C, without permanent bonding of the glass carrier and glass thin sheet.

In Examples 4a-4e above, each carrier and thin sheet was Eagle XG® glass, where the carrier was a 150 mm diameter SMF wafer 630 micrometer thick and the thin sheet was 100 square mm 100 micrometer thick. The silane layer was a self-assembled monolayer (SAM), and thus was less than about 2 nm thick. In this example, SAM was generated using organosilanes with aryl or alkyl nonpolar tail groups and mono, di, or tri-alkoxide head groups. They react with the silanol surface of the glass to directly attach the organic functional groups. The weaker interaction between the non-polar head groups constitutes the organic layer. Due to the small thickness in the surface modification layer, there is less risk of gas evolution which can lead to contamination during device fabrication. Also, the risk of outgassing is less because the surface modification layer did not appear to decompose once more in Examples 4c, 4d, and 4e. In addition, as shown in Table 4, each glass thin sheet was cleaned using the SC1 process before heat treatment under vacuum at 400° C. for one hour.

As can be seen from the comparison of Examples 4a-4e, controlling the surface energy of the bonding surface to be greater than 40 mJ/m 2 to promote initial room temperature bonding will withstand FPD processing and yet thin sheets will be removed from the carrier without damage. It's not just a discussion of creating controlled bindings that will enable you to do so. In particular, as can be seen from Examples 4a-4e, each carrier had a surface energy greater than 40 mJ/m 2, which promoted the initial room temperature bonding to allow the article to withstand vacuum and SRD processing. However, Examples 4a and 4b did not pass the 600°C processing test. As mentioned above, for certain applications, the bonding is processed to a high temperature or less (e.g., ≥ 400°C, ≥ 500°C, or ≥600°C, 650°C or less, suitable for processes designed to allow the article to be used) It is also important to hold the thin sheet and carrier together without decomposition of the bond, and also tolerate to the point where it is insufficient to control the covalent bonding occurring at such high temperatures so that there is no permanent bond between the thin sheet and the carrier. As shown by the examples in Table 4, aromatic silanes, especially phenyl silanes, will promote initial room temperature bonding and withstand FPD processing, but still provide controlled bonding that allows thin sheets to be removed from the carrier without damage. Useful for providing.

The separations described above in Examples 4, 3, and 2 are performed at room temperature without the addition of any additional heat or chemical energy that modifies the bonding interface between the thin sheet and the carrier. The only energy input is mechanical pulling and/or peeling force.

The materials described above in Examples 3 and 4 can be applied to a carrier, to a thin sheet, or to both a carrier and a thin sheet surface to be joined together.

Use of controlled coupling

Reusable carrier

One use of bonding controlled via a surface modification layer (including material and associated bonding surface heat treatment) is to provide reuse of carriers in articles that have undergone a process requiring a temperature of ≥ 600° C., such as in LTPS processing, for example. will be. Surface modification layers (including materials and bonding surface heat treatments), as exemplified by Examples 2e, 3a, 3b, 4c, 4d, and 4e above can be used to provide reuse of carriers under such temperature conditions. In particular, the surface modification layer can be used to change the surface energy of the overlapping region between the thin sheet and the bonding region of the carrier, whereby the entire thin sheet can be separated from the carrier after processing. The thin sheets can all be separated at once, or they can be separated, for example, by first removing the device made on a portion of the thin sheet and then removing the remaining portion to clean the carrier for reuse. It might be. When the entire thin sheet is removed from the carrier, the carrier can be reused as is by simply placing another thin sheet over the carrier. Alternatively, the carrier can be prepared to have a thinner sheet once again by cleaning and re-forming the surface modification layer. Since the surface modification layer prevents permanent bonding of the carrier and the thin sheet, they can be used in processes where the temperature is ≥ 600°C. Of course, these surface modification layers can control the bonding surface energy during processing at a temperature of ≥ 600°C, but they can also be used to produce thin sheet and carrier combinations that will withstand processing at lower temperatures, such lower temperatures It can be used to control binding in applications. In addition, if the thermal processing of the article does not exceed 400° C., a surface modification layer as exemplified by Examples 2c, 2d, 4b can also be used in this same way.

To provide a controlled bonding area

The second use of controlled bonding through the surface modification layer (including material and associated bonding surface heat treatment) is to provide a controlled bonding region between the glass carrier and the glass thin sheet. More particularly, the use of a surface modification layer allows sufficient separation force to separate the thin sheet portion from the carrier without damage to the thin sheet or carrier caused by bonding, but sufficient binding force to hold the thin sheet against the carrier is achieved throughout processing. It can form a region of controlled bond that is maintained across. Referring to FIG. 6, the glass thin sheet 20 can be bonded to the glass carrier 10 by the joined region 40. In the bonded region 40, the carrier 10 and the thin sheet 20 are covalently bonded to each other to act as monoliths. In addition, there is a controlled bonding area 50 with a perimeter 52, where the carrier 10 and the thin sheet 20 are connected, but from each other even after high temperature processing, for example processing at a temperature of ≥ 600°C. Can be separated. Ten controlled binding regions 50 are shown in FIG. 6, but can provide any suitable number, including one. Carrier 10 and thin sheet using surface modification layer 30, including material and bonding surface heat treatment, as illustrated by Examples 2a, 2e, 3a, 3b, 4c, 4d, and 4e above ( 20) A controlled bonding region 50 can be provided between. In particular, this surface modification layer can be formed in the periphery 52 of the carrier 10 or the controlled bonding region 50 of the thin sheet 20. Thus, when the article 2 is processed at a high temperature to form a covalent bond in the bonding region 40 or during device processing, control between the carrier 10 and the thin sheet 20 within the region limited by the peripheral portion 52 Bonded bonds can be provided, whereby the separating force can separate the thin sheets and carriers in this zone (without catastrophic damage to the thin sheets or carriers), but the thin sheets and carriers will not peel off during processing, including ultrasonic processing. . The controlled bonding of the present application, as provided by the surface modification layer and any associated heat treatment, can thus be improved based on the carrier concept of US '727. In particular, the carriers of US '727 have been proven to withstand FPD processing, including high temperature processing of ≥ about 600°C, with their bonded periphery and non-bonding central zones, but ultrasonic processing, such as wet clean and resist strip processing, continues It is challenging. In particular, pressure waves in solution have been shown to induce synchronic vibrations in thin glass in a non-bonding zone (non-bonding is as described in US '727), where the adhesion to bond the thin glass and carrier to that zone is nearly Because there was none or none. Standing waves can be formed in the thin glass, and these waves can cause vibrations that can cause destruction of the thin glass at the interface between the bonded and non-bonded zones if ultrasonic agitation has sufficient strength. This problem can be eliminated by minimizing the gap between the thin glass and the carrier and providing a controlled bond between the carrier 20 and the thin glass 10 in these areas 50, or sufficient adhesion. The surface modification layer of the bonding surface (including materials as exemplified by Examples 2a, 2e, 3a, 3b, 4c, 4d, and 4e, and any associated heat treatment) is provided between the thin sheet 20 and the carrier 10. The binding energy is controlled to prevent this unwanted vibration in the controlled coupling zone by providing sufficient coupling of the.

Subsequently, while tearing off the necessary portion 56 with the periphery 57, a portion of the thin sheet 20 in the periphery 52 is removed after processing and after separating the thin sheet along the periphery 57, the carrier 10 Can be simply separated from. Since the surface modification layer controls the binding energy to prevent permanent bonding of the carrier and the thin sheet, they can be used in processes where the temperature is ≥ 600°C. Of course, these surface modification layers can control the bonding surface energy during processing at a temperature of ≥ 600°C, but they can also be used to produce thin sheet and carrier combinations that will withstand processing at lower temperatures, such lower temperatures It can be used in applications. In addition, if the thermal processing of the article does not exceed 400° C., the surface modification layer as exemplified by Examples 2c, 2d, 4b is also in this same way-in some cases according to different process requirements-the bonding surface. Can be used to control energy.

To provide a bonding area

The third use of controlled bonding through surface modification layers (including material and any associated bonding surface heat treatment) is to provide a bonding region between the glass carrier and the glass thin sheet. Referring to FIG. 6, the glass thin sheet 20 can be bonded to the glass carrier 10 by the joined region 40.

In one embodiment of the third use, in the bonded region 40, the carrier 10 and the thin sheet 20 can be covalently bonded to each other to act as monoliths. In addition, there is a controlled bonding region 50 with a perimeter 52, where the carrier 10 and the thin sheet 20 are sufficient to withstand processing, but still at high temperature processing, for example at a temperature of ≥ 600°C. They are joined together to allow separation of the thin sheet from the carrier even after processing. Thus, the carrier 10 using the surface modification layer 30 (including material and bonding surface heat treatment) as illustrated by Examples 1a, 1b, 1c, 2b, 2c, 2d, 4a, and 4b above, and It is possible to provide a bonding region 40 between the thin sheets 20. In particular, this surface modification layer and heat treatment can be formed outside the perimeter 52 of the carrier 10 or the controlled bonding region 50 of the thin sheet 20. Thus, when the article 2 is processed at a high temperature or is processed at a high temperature to form a covalent bond, the carrier and the thin sheet 20 are bonded to each other within the bonding region 40 outside the region limited by the peripheral portion 52. Will be. Subsequently, if it is desired to dice the thin sheet 20 and the carrier 10 while tearing off the necessary portion 56 having the periphery 57, this surface modification layer and heat treatment is applied to the thin sheet 20 And the article can be separated along line 5 as it covalently bonds with carrier 10 and acts as a monolith in this region. Since the surface modification layer provides a permanent covalent bond between the carrier and the thin sheet, they can be used in processes where the temperature is ≥ 600°C. In addition, if the thermal processing of the initial formation of the article, or bonding region 40 is ≥ 400°C or less than 600°C, the surface modification layer, as exemplified by the material and heat treatment in Example 4a, may also be used in this same manner. Can be used.

In the second embodiment of the third use, in the bonded region 40, the carrier 10 and the thin sheet 20 can be bonded to each other by controlled bonding through the various surface modification layers described above. In addition, there is a controlled bonding area 50, with a perimeter 52, where the carrier 10 and the thin sheet 20 are sufficient to withstand processing, yet at high temperature processing, for example at a temperature of ≥ 600°C. It is bonded to each other to allow separation of the thin sheet from the carrier even after processing. Thus, processing will be performed at a temperature of 600° C. or less, and if it is desired to have no permanent or covalent bonds in the region 40, illustrated by Examples 2e, 3a, 3b, 4c, 4d, and 4e above The surface modification layer 30 (including material and bonding surface heat treatment) can be used to provide a bonding region 40 between the carrier 10 and the thin sheet 20. In particular, this surface modification layer and heat treatment can be formed outside the periphery 52 of the controlled bonding region 50 and can be formed on the carrier 10 or on the thin sheet 20. The controlled bonding region 50 can be formed of the same or different surface modification layers that were formed in the bonding region 40. Alternatively, the processing will be performed only at a temperature of 400° C. or less, and if it is desired to have no permanent or covalent bonds in the region 40, the above Examples 2c, 2d, 2e, 3a, 3b, 4b, 4c A surface modification layer 30 (including material and bonding surface heat treatment) as illustrated by 4d, 4e can be used to provide a bonding region 40 between the carrier 10 and the thin sheet 20. .

Instead of controlled binding to region 50, there may be a non-binding region in region 50, where the non-binding region may be a region with increased surface roughness as described in US '727, or implemented A surface modification layer as illustrated by Example 2a can be provided.

For the manufacture of electronic devices

The fifth use of controlled bonding, as described herein, is to manufacture glass articles, including glass articles with carriers and thin sheets bonded to them, which, in turn, result in electronic devices, such as TFTs. , OLEDs (including organic light emitting materials), PV devices, touch sensors, and displays. Reusable carriers can be used, for example, as described above. Alternatively, glass articles having bonded and controlled bonding regions can be used, for example as described above.

In any case, electronic device processing equipment as currently designed for thicker sheets can be used to process glass articles to place electronic-device components, or parts of electronic devices, on sheets of articles. The electronic device component should be placed on a portion(s) of the thin sheet bonded to the carrier through the controlled coupling described above, whereby the thin sheet remains detachable from the carrier even after processing to the temperature required to manufacture the electronic device. Remains. Device processing may include, for example, processing at temperatures of ≥ 400°C, ≥ 500°C, ≥ 600°C, or 650°C or less. As described above, a suitable surface modification layer remains removable from the carrier, even after the thin sheet has been processed to such a temperature-at least without damage to the thin sheet, and preferably without damage to both the thin sheet and the carrier. So it can be chosen. Any number of electronic-device components can be deployed at any number of steps to do so, until the electronic device is complete or at an appropriate intermediate stage. The article can be assembled prior to processing the electronic device, or can be assembled as part of the electronic device manufacturing process.

Device processing can include keeping the article intact throughout the entire device processing, or can include dicing the item at one or more points in the process. For example, device processing forms one electronic-device component on an article, and then dices the article into two or more portions and then sheets additional components of the electronic device from further processing, ie, the placement of the previous step. And on the electronic-device component present on the sheet. The dicing step can be performed to include a portion of the thin sheet where each portion of the article remains attached to the carrier, or only a subset of the diced portion to include such an arrangement. Within any diced portion, the entire region of the thin sheet at that portion may remain bound to the entire region of the carrier at that portion.

After processing the device as a finished product or in an intermediate step, the device and a portion of the thin sheet on which the device is placed can be removed from the carrier. The thin sheet may be entirely removed, or a portion of it may be separated from the remaining portion and the portion removed from the carrier. Removal can take place entirely from the article, or from one or more portions diced from it.

Gas emission

Polymer adhesives used in typical wafer bonding applications are generally 10-100 micrometers thick and lose about 5% of their mass at or near its temperature limit. For such materials, generated in thick polymer films, it is easy to quantify the amount of mass loss, or gas evolution, by mass-analysis. On the other hand, it is more challenging to measure gas release by a thin surface treatment of approximately 10 nm or less in thickness, for example from the plasma polymer or self-assembled monolayer surface modification layer described above, as well as by a thin layer of pyrolized silicone oil. to be. For such materials, mass-spectroscopy is not sensitive enough. However, there are many other ways to measure gas emissions.

The first method of measuring a small amount of gas emission is based on surface energy measurement and will be described with reference to FIG. 7. To perform this test, a setup as shown in FIG. 7 can be used. The first substrate, or carrier 900, having a surface modification layer to be tested above provides a surface 902, ie, the surface modification layer corresponds in composition and thickness to the surface modification layer 30 to be tested. The second substrate, or cover 910 is placed such that its surface 912 is adjacent to, but not in contact with, the surface 902 of the carrier 900. Surface 912 is the uncoated surface, that is, the surface of the bare material from which the cover is made. The spacer 920 lies at various points between the carrier 900 and the cover 910 and keeps them spaced apart from each other. The spacer 920 is thick enough to separate the cover 910 from the carrier 900 to allow material to move from one to the other, but the amount of contamination from the chamber atmosphere at the surfaces 902 and 912 during the test. It should be thin enough to minimize. The carrier 900, spacer 920, and cover 910 together form a test article 901.

Before assembling the test article 901, the surface energy of the bare surface 912 is measured, as is the surface energy of the surface 902, that is, the surface of the carrier 900 having a surface modification layer provided over the carrier. The surface energy, polarity and dispersion component as shown in FIG. 8 are both S. The theoretical model developed by S. Wu (1971) was tested for three liquids; It was measured by fitting to three contact angles of water, diiodomethane and hexadecane. (Reference: S. Wu, J. Polym. Sci. C, 34, 19, 1971).

After assembly, the test article 901 is placed in a heating chamber 930 and heated throughout the time-temperature cycle. Heating is carried out at atmospheric pressure and under flowing N2 gas, ie under N2 gas flowing in the direction of arrow 940 at a rate of 2 standard liters/minute.

During the heating cycle, changes in the surface 902 (including, for example, changes to the surface modification layer due to evaporation, pyrolysis, decomposition, polymerization, reaction with the carrier, and dewetting) are the surface energy of the surface 902 It is indicated by a change in Esau. The change in the surface energy of the surface 902 itself does not necessarily mean that the surface modification layer has been gas released, but exhibits the general instability of the material at that temperature since its properties are changing, for example due to the mechanisms mentioned above. Thus, the less change in surface energy of surface 902, the more stable the surface modification layer. On the other hand, due to the proximity of the surface 912 to the surface 902, any material that is gas released from the surface 902 will collect on the surface 912 and change the surface energy of the surface 912. will be. Thus, a change in surface energy of surface 912 becomes a proxy for outgassing of the surface modification layer present at surface 902.

Thus, one test for gas evolution utilizes a change in surface energy of the cover surface 912. Specifically, if there is a change in surface energy-of surface 912 -≧10 mJ/m 2, then there is gas evolution. Changes in surface energy at this scale are consistent with contamination that can lead to loss or degradation of film adhesion in material properties and device performance. The change in surface energy of ≤ 5 mJ/m 2 is close to the repeatability of surface energy measurement and the nonuniformity of surface energy. This small change is consistent with minimal outgassing.

During the test that resulted in FIG. 8, the carrier 900, cover 910, and spacer 920 were Eagle XG glass, alkali-free alumino- available from Corning, Corning, NY. Although made of boro-silicate display-grade glass, it need not be true. The carrier 900 and cover 910 were 150 mm diameter 0.63 mm thick. Generally, the carrier 910 and the cover 920 will be made of the same material as the carrier 10 and the thin sheet 20, respectively, where gas release testing is required. During this test, the silicon spacer was 0.63 mm thick, 2 mm wide, and 8 cm long, thereby forming a gap of 0.63 mm between the surfaces 902 and 912. During this test, the chamber 930 was cycled from room temperature to the test limit temperature at a rate of 9.2° C./min, held at the test limit temperature for various times as indicated by the “anneal time” in the graph, followed by a furnace speed of 200 MPT-RTP600s cooled to °C were included in the rapid thermal processing equipment. After cooling the oven to 200° C., the test article was removed, and after the test article was cooled to room temperature, the surface energy of each surface 902 and 912 was measured once more. Thus, for example, for material #1, using data on changes in cover surface energy, line 1003, tested at a limit temperature of 450° C., data were collected as follows. The data point at 0 min represents a surface energy of 75 mJ/m 2 (milli-joules/square meter) and is the surface energy of the bare glass, ie there has not been a time-temperature cycle yet to be performed. The data point at 1 minute represents the surface energy as measured after the time-temperature cycling performed as follows: (with material #1 used as surface modification layer on carrier 900 to provide surface 902) ) The article 901 was placed in the heating chamber 930 at room temperature, and atmospheric pressure; The chamber was heated to a test-limit temperature of 450° C., even at a rate of 9.2° C./min, under a 2 standard liter/min N 2 gas flow, and held for 1 minute at a test-limit temperature of 450° C.; The chamber could then be cooled to 300° C. at a rate of 1° C./min, and then the article 901 was removed from the chamber 930; The article could then be cooled to room temperature (without N2 flowing atmosphere); The surface energy of surface 912 was then measured and plotted on line 1003 as a point for 1 minute. Subsequent data points for material #1 (line (1003), (1004)), as well as material #2 (line (1203), (1204)), material #3 (line (1303), (1304)) , Data points for substance #4 (line 1403, 1404), substance #5 (line 1503, 1504), and substance #6 (line 1603, and 1604), Appropriately, the minutes of the annealing time were determined by a similar method corresponding to the test-limit temperature, holding time at 450°C, or 600°C. Lines (1001), (1002), (1201), (1202), (1301), (1302), representing the surface energy of the surface 902 for the corresponding surface modification layer material (Material #1-6) Data points for, (1401), (1402), (1501), (1502), (1601), and (1602), excluding the surface energy of the surface 902 measured after each time-temperature cycle And decided in a similar way.

The assembly process, and time-temperature cycling were performed on six different materials as described below, and the results are graphed in FIG. 8. Of the six materials, material #1-4 corresponds to the surface modification layer material described above. Materials #5 and #6 are comparative examples.

Material #1 is CHF3-CF4 plasma polymerized fluoropolymer. This material is consistent with the surface modification layer in Example 3b above. As shown in FIG. 8, lines 1001 and 1002 show that the surface energy of the carrier has not changed significantly. Therefore, this material is very stable at temperatures between 450°C and 600°C. In addition, as indicated by lines 1003 and 1004, the surface energy of the cover did not change significantly, that is, the change was ≦5 mJ/m 2. Thus, there was no outgassing associated with this material at 450°C to 600°C.

Material #2 is a self-assembled monolayer (SAM), phenylsilane, deposited from a 1% toluene solution of phenyltriethoxysilane and cured at 190° C. for 30 minutes in a vacuum oven. This material is consistent with the surface modification layer of Example 4c above. As shown in FIG. 8, lines 1201 and 1202 indicate slight changes in the surface energy of the carrier. As mentioned above, this shows some change in the surface modification layer, and in comparison, material #2 is somewhat less stable than material #1. However, as noted by lines 1203 and 1204, the change in the surface energy of the carrier is ≦5 mJ/m 2 and shows that the change to the surface modification layer did not cause gas evolution.

Material #3 is SAM, pentafluorophenylsilane, deposited from a 1% toluene solution of pentafluorophenyltriethoxysilane and cured at 190° C. for 30 minutes in a vacuum oven. This material is consistent with the surface modification layer of Example 4e above. As shown in FIG. 8, lines 1301 and 1302 indicate a slight change in the surface energy of the carrier. As mentioned above, this indicates a slight change in the surface modification layer, and in comparison, material #3 is somewhat less stable than material #1. However, as noted by lines 1303 and 1304, the change in the surface energy of the carrier is ≦5 mJ/m 2 and shows that the change to the surface modification layer did not cause gas evolution.

Material #4 is hexamethyldisilazane (HMDS) deposited from steam at 140° C. in a YES HMDS oven. This material is consistent with the surface modification layer of Example 2b in Table 2 above. As shown in FIG. 8, lines 1401 and 1402 represent a slight change in the surface energy of the carrier. As noted above, this shows a slight change in the surface modification layer and, by comparison, material #4 is somewhat less stable than material #1. In addition, the change in the surface energy of the carrier for material #4 is greater than that of any of materials #2 and #3, and, in comparison, indicates that material #4 is somewhat less stable than materials #2 and #3. However, as noted by lines 1403 and 1404, the change in the surface energy of the carrier is ≦5 mJ/m 2, and the change to the surface modification layer does not cause gas evolution that has affected the surface energy of the cover. Shows that it was not. However, this is consistent with the way HMDS emits gases. In other words, HMDS releases ammonia and water that do not affect the surface energy of the cover and cannot affect some electronics manufacturing equipment and/or processing. On the other hand, if the product of gas evolution is trapped between a thin sheet and a carrier, there may be other problems, as mentioned below in connection with the secondary gas emission test.

Material #5 is SAM, glycidoxypropylsilane, deposited from a 1% toluene solution of glycidoxypropyltriethoxysilane and cured at 190°C for 30 minutes in a vacuum oven. This is a comparative example material. As indicated by lines 1501 and 1502, there is a relatively small change in the surface energy of the carrier, but as shown by lines 1503 and 1504, there is a significant change in the surface energy of the cover. That is, although material #5 was relatively stable at the carrier surface, it actually outgassed a significant amount of material on the cover surface, and the cover surface energy was changed by ≥ 10 mJ/m 2. The surface energy is within 10 mJ/m 2 at the end of 10 minutes at 600° C., but the change during that time exceeds 10 mJ/m 2. See for example data points at 1 and 5 minutes. While not wishing to be bound by theory, a slight increase in surface energy between 5 and 10 minutes is likely to cause some of the outgassed material to decompose and fall off the cover surface.

Material #6 was prepared by dispensing 5 ml Dow Corning 704 diffusion pump oil tetramethyltetraphenyl trisiloxane (available from Dow Corning) onto a carrier and placing it in an air in a 500° C. hot plate for 8 minutes. It is silicone coated DC704. The completion of sample preparation is noted by the end of the visible smoke. After the sample was prepared by the above method, the gas release test described above was performed. This is a comparative example material. As shown in FIG. 8, lines 1601 and 1602 indicate a slight change in the surface energy of the carrier. As mentioned above, this indicates a slight change in the surface modification layer, and in comparison, material #6 is less stable than material #1. In addition, as noted by lines 1603 and 1604, the change in surface energy of the carrier is ≥ 10 mJ/m 2, indicating significant gas evolution. More particularly, at a test-limit temperature of 450° C., the data point for 10 minutes shows a decrease in surface energy of about 15 mJ/m 2, and for data points at 1 and 5 minutes, a much greater decrease in surface energy. Indicates. Similarly, the decrease in the surface energy of the cover, which is a change in the surface energy of the cover during cycling at 600° C. test-limit temperature, was about 25 mJ/m 2 at the 10 minute data point, slightly larger at 5 minutes, 1 In minutes it was somewhat less. Overall, a significant amount of outgassing was seen for this material over the entire range of tests.

Significantly, for material #1-4, the surface energy across the time-temperature cycle continues to be at the surface energy where the cover surface matches the surface energy of the bare glass, ie, the collected material that has been released from the carrier surface This shows no. For material #4, as mentioned in relation to Table 2, the manner in which the carrier and thin sheet surfaces are prepared depends on whether the article (thin sheet bonded with the carrier via the surface modification layer) will withstand FPD processing. There is a big difference. Thus, although the embodiment of Material #4 shown in FIG. 8 is not gaseous, this material may or may not withstand a 400° C. or 600° C. test as noted in connection with the discussion in Table 2.

The second method of measuring a small amount of gas release is based on the assembled article, ie a thin sheet is bonded to the carrier via a surface modification layer, and uses a change in percent bubble area to determine gas evolution. That is, while heating the article, bubbles formed between the carrier and the thin sheet indicate outgassing of the surface modification layer. As mentioned above with regard to the primary gas evolution test, it is difficult to measure the gas evolution of a very thin surface modification layer. In this secondary test, gas evolution under the thin sheet can be limited by the strong adhesion between the thin sheet and the carrier. Nevertheless, a layer of <10 nm thickness (e.g., plasma polymerized material, SAM, and pyrolized silicone oil surface treatment), despite its less absolute mass loss, will continue to generate bubbles during heat treatment. Can be. And the creation of bubbles between the thin sheet and the carrier can cause problems associated with pattern generation, photolithography processing, and/or alignment during device processing on the thin sheet. In addition, bubbling at the boundary of the bonded area between the thin sheet and the carrier can cause problems with process fluids from one process that contaminate downstream processes. Changes in the% bubble region of ≧5, indicating outgassing are important and undesirable. On the other hand, the change in the% bubble region of ≦1 is not significant and is an indication that there was no outgassing.

The average bubble area of thin glass bonded by manual bonding in a grade 1000 clean room is 1%. The% bubble in the combined carrier is a function of the cleanliness of the carrier, thin glass sheet, and surface preparation. Since these initial defects act as nucleation sites for bubble growth after heat treatment, any change in the bubble area of less than 1% upon heat treatment is within the variability of sample preparation. To perform this test, a first scan image of a region combining thin sheets and carriers immediately after binding was made using a commercially available desktop scanner with a perspective view unit (Epson Expression 10000XL Photo). A portion was scanned using standard Epson software and using 508 dpi (50 micrometers/pixel) and 24 bit RGB. The image processing software first prepares the image by stitching the images of different sections of the sample into a single image, if necessary, and removing the scanner artifacts (using a black reference scan performed without samples on the scanner). The bound regions are then analyzed using standard imaging techniques, such as thresholding, hole filling, erosion/delation, and blob analysis. The newer Epson Expression 11000XL photo can also be used in a similar way. In the transmission mode, bubbles in the combined region are visible in the scanned image and the value for the bubble region can be determined. The bubble area is then compared to the total bonding area (i.e., the total overlapping area between the thin sheet and the carrier) to calculate the% area of the bubble in the bonding area relative to the total bonding area. The sample is then heat treated in an MPT-RTP600s rapid thermal processing system under test-limit temperatures of 300° C., 450° C., and 600° C. under N 2 atmosphere for 10 minutes or less. Specifically, the time-temperature cycling performed was: the article was inserted into the heating chamber at room temperature and atmospheric pressure; The chamber was then heated to a test-limit temperature at a rate of 9° C./minute; The chamber was maintained at the test-limit temperature for 10 minutes; The chamber was then cooled to 200° C. at the furnace rate; The article could be removed from the chamber and allowed to cool to room temperature; This included scanning the article back to the optical scanner. The% bubble area from the second scan was then calculated as above and the change in% bubble area (Δ% bubble area) was determined compared to the% bubble area from the first scan. As mentioned above, the change in bubble area of ≧5% is important and an indication of gas evolution. The change in% bubble region was originally chosen as a measurement criterion due to variability in the% bubble region. That is, most surface modification layers have a bubble area of about 2% in the first scan due to handling and cleanliness after preparing thin sheets and carriers and before joining them. However, changes can occur between materials. The same material #1-6 described in relation to the primary gas emission test method was used once more in the secondary gas emission test method. Of these materials, material #1-4 showed about 2% bubble area in the first scan, while materials #5 and #6 showed significantly larger bubble areas in the first scan, i.e. about 4%.

The results of the secondary gas release test will be explained with reference to FIGS. 9 and 10. The results of the gas evolution test for material #1-3 are shown in Figure 9, while the results of the gas emission test for material #4-6 are shown in Figure 10.

Results for material #1 are shown in FIG. 9 as square data points. As can be seen from the figure, the change in% bubble region was close to zero for test-limit temperatures of 300°C, 450°C, and 600°C. Thus, material #1 does not exhibit gas evolution at these temperatures.

The results for Material #2 are shown in FIG. 9 as rhombus data points. As can be seen from the figure, the change in% bubble area is less than 1 for test-limit temperatures of 450°C and 600°C. Thus, material #2 does not exhibit gas evolution at these temperatures.

The results for Material #3 are shown in FIG. 9 as triangle data points. As can be seen from the figure, similar to the results for material #1, the change in% bubble region was close to zero for test-limit temperatures of 300°C, 450°C, and 600°C. Thus, material #1 does not exhibit gas evolution at these temperatures.

Results for material #4 are shown in FIG. 10 as circular data points. As can be seen from the figure, the change in% bubble area is close to 0 for the test-limit temperature of 300°C, but close to 1% for the test-limit temperature of 450°C and 600°C for some samples, For other samples of the same material it is about 5% at the test-limit temperatures of 450°C and 600°C. The results for material #4 are very inconsistent and depend on how the thin sheet and carrier surfaces are prepared for bonding with the HMDS material. The manner in which sample performance depends on the manner in which the sample is prepared is consistent with the examples of these materials described in relation to Table 2 above, and the related discussion. For this material, samples with a change in the% bubble region close to 1% for the 450°C and 600°C test-limit temperatures did not allow separation of the thin sheet from the carrier according to the separation test described above. I noticed. That is, strong adhesion between the thin sheet and the carrier may have limited the generation of bubbles. On the other hand, samples with a change in% bubble area close to 5% allowed separation of the thin sheet from the carrier. Thus, samples that did not have gas evolution had undesirable results of increased adhesion (preventing the removal of the thin sheet from the carrier) after temperature treatment of sticking the carrier and the thin sheet together, while allowing removal of the thin sheet and the carrier. The sample had undesirable results of gas evolution.

The results for Material #5 are shown in FIG. 10 as triangle data points. As can be seen from the figure, the change in% bubble area is about 15% for the test-limit temperature of 300°C and significantly exceeds that for the higher test-limit temperatures of 450°C and 600°C. Thus, material #5 exhibits significant gas evolution at these temperatures.

Results for material #6 are shown in FIG. 10 as square data points. As can be seen from this figure, the change in% bubble region is greater than 2.5% for the test-limit temperature of 300°C, and more than 5% for the test-limit temperature of 450°C and 600°C. Thus, Material #6 shows significant gas release at the test-limit temperatures of 450°C and 600°C.

conclusion

It should be emphasized that the above-described embodiments of the present invention, particularly any “preferred” embodiments, are merely feasible embodiments and are merely described for a solid understanding of the various principles of the present invention. Many variations and modifications can be made to the above-described embodiments of the invention without substantially departing from the spirit and various principles of the invention. All such modifications and variations are intended to be included within the scope of this disclosure and the invention herein and protected by the following claims.

For example, the surface modification layer 30 of many embodiments has been shown and discussed to be formed on the carrier 10, but may alternatively or additionally be formed on the thin sheet 20. That is, the materials as described in Examples 4 and 3 can be applied to the carrier 10 of the side to be joined together, to the thin sheet 20, or to both the carrier 10 and the thin sheet 20. .

In addition, although some surface modification layer 30 is described as controlling the bond strength so that the thin sheet 20 can be removed from the carrier 10 even after the article 2 is processed at a temperature of 400° C., or 600° C. Of course, the article 2 can be processed at a temperature lower than the temperature of the particular test the article has passed, and the thin sheet 20 can be carrier 10 without still damaging the thin sheet 20 or carrier 10. The same ability to remove from can be achieved.

Additionally, although the controlled bonding concept has been described herein as being usable with carriers and thin sheets, in certain situations they can be applied to control bonding between glass, ceramic, or thicker sheets of glass ceramic, and sheet It may be required to separate (or portions of) one another.

Additionally, while the controlled bonding concept has been described herein as useful with glass carriers and glass thin sheets, the carriers can be made of other materials, such as ceramics, glass ceramics, or metals. Similarly, the sheet controllably coupled to the carrier can be made of other materials, such as ceramic or glass ceramic.

The various above-described concepts according to the present application can be combined with each other in any and all different ways in combination. For example, various concepts can be combined according to the following aspects.

According to the first aspect,

Obtaining a carrier having a carrier binding surface;

A sheet having a sheet bonding surface was obtained;

Placing a surface modification layer on one of the carrier bonding surface and the sheet bonding surface;

The carrier bonding surface and the sheet bonding surface are joined with a surface modification layer between them to form an article, but the surface energy to bond the sheet to the carrier is:

Temperature cycling is applied to the article by heating it in a chamber that is circulated from room temperature to 600 °C at a rate of 9.2 °C/min, held at a temperature of 600 °C for 10 minutes, and then cooled to 300 °C at 1 °C/min, After the article is then removed from the chamber and allowed to cool the article to room temperature, the carrier and sheet are retained and the other is not separated from each other when subjected to gravitational force, and gas is released from the surface modification layer during the temperature cycling Without this, and the thinner of the carrier and the sheet is formed so as to have a feature that allows the sheet to be separated from the carrier without breaking into two or more fragments;

Placing electronic-device components on the sheet

A method of manufacturing an electronic device is provided.

According to the second aspect,

A carrier having a carrier bonding surface;

A sheet having a sheet bonding surface;

A surface modification layer disposed on one of the carrier bonding surface and the sheet bonding surface

A glass article comprising:

The carrier bonding surface and the sheet bonding surface are bonded with a surface modification layer between them, where the surface energy that bonds the sheet to the carrier is,

Temperature cycling is applied to the article by heating it in a chamber that is circulated from room temperature to 600 °C at a rate of 9.2 °C/min, held at a temperature of 600 °C for 10 minutes, and then cooled to 300 °C at 1 °C/min, After the article is then removed from the chamber and allowed to cool the article to room temperature, the carrier and sheet are retained and the other is not separated from each other when subjected to gravitational force, and gas is released from the surface modification layer during the temperature cycling Without this, the thinner of the carrier and the sheet has the feature that allows the sheet to be separated from the carrier without breaking into two or more fragments,

Obtaining glass articles;

Placing electronic-device components on the sheet

A method of manufacturing an electronic device is provided.

According to a third aspect, a method of aspect 1 or aspect 2 is provided, wherein the electronic device component comprises an organic light emitting material.

According to a fourth aspect, a method of any one of aspects 1 to 3 is provided, wherein processing the electronic device comprises processing at a temperature of ≧400° C.

According to a fifth aspect, a method of any one of aspects 1 to 3 is provided, wherein processing the electronic device comprises processing at a temperature of ≥ 600°C.

According to a sixth aspect, a method of any one of aspects 1 to 5 is provided, further comprising dicing the carrier and the sheet into two separate parts.

According to a seventh aspect, a method of aspect 6 is provided, wherein at least one of the discrete portions comprises a sheet portion that remains coupled to the carrier portion.

According to an eighth aspect, a method of aspect 6 or aspect 7 is further provided, further comprising further processing at least one of the separate portions with an additional electronic-device component.

According to a ninth aspect, the method of any one of aspects 1 to 8, further comprising removing at least a portion of the sheet from the carrier, wherein at least a portion of the sheet comprises electronic device components thereon. Is provided.

According to a tenth aspect, a method of any one of aspects 1 to 9 is provided, wherein the carrier comprises glass.

According to an eleventh aspect, a method of any one of aspects 1-10 is provided, wherein the carrier without any surface modification layer has an average surface roughness Ra of ≦2 nm.

According to a twelfth aspect, a method of any one of aspects 1-11 is provided, wherein the carrier has a thickness of 200 micrometers to 3 mm.

According to a thirteenth aspect, a method of any one of aspects 1-12 is provided, wherein the sheet comprises glass.

According to a fourteenth aspect, a method of any one of aspects 1-13 is provided, wherein the sheet without any surface modification layer has an average surface roughness Ra of ≦2 nm.

According to a fifteenth aspect, a method of any one of aspects 1 to 14 is provided, wherein the sheet has a thickness of ≦300 micrometers.

According to a sixteenth aspect, a method of any one of aspects 1 to 15 is provided, wherein the surface modification layer has a thickness of 0.1 to 100 nm.

According to a seventeenth aspect, a method of any one of aspects 1 to 15 is provided, wherein the surface modification layer has a thickness of 0.1 to 10 nm.

According to the eighteenth aspect, a method of any one of the aspects 1 to 15 is provided, wherein the surface modification layer has a thickness of 0.1 to 2 nm.

According to a nineteenth aspect, a method of any one of aspects 1 to 18 is provided, wherein each carrier and sheet has a size of 100 mm×100 mm or more.

According to the twentieth aspect, the surface modification layer

a) plasma polymerized fluoropolymers; And

b) aromatic silane

A method of any one of aspects 1 to 19 is provided, comprising any of the following.

According to a twenty-first aspect, when the surface modification layer comprises a plasma-polymerized fluoropolymer, the surface modification layer is plasma-polymerized polytetrafluoroethylene; And one of the plasma polymerized fluoropolymer surface modification layers deposited from a CF4-C4F8 mixture having <40% C4F8.

According to a twenty-second aspect, when the surface modification layer comprises an aromatic silane, the surface modification layer may include phenyltriethoxysilane; Diphenyldiethoxysilane; And 4-pentafluorophenyltriethoxysilane. The method of aspect 20 is provided.

According to a twenty-third aspect, the method of aspect 20 is provided, wherein the surface modification layer contains a chlorophenyl silyl group or a fluorophenyl silyl group when the surface modification layer comprises an aromatic silane.

Claims (20)

Obtaining a carrier having a carrier binding surface;
A sheet having a sheet bonding surface was obtained;
Placing a surface modification layer on one of the carrier bonding surface and the sheet bonding surface;
The carrier bonding surface and the sheet bonding surface are bonded with a surface modification layer between them to form an article, but the surface energy for bonding the sheet to the carrier is circulated from room temperature to 600°C at a rate of 9.2°C/min, 600°C After maintaining the temperature for 10 minutes, and then heating the article in a chamber cooled to 300° C. at 1° C./minute, applying temperature circulation to the article, and then removing the article from the chamber and allowing the article to cool to room temperature, The carrier and sheet are retained and the other is not separated from each other when subjected to gravitational force, there is no gas release from the surface modification layer during the temperature cycling, and the thinner of the carrier and sheet is broken into two or more pieces without breaking Is formed so as to have features that enable it to be separated from the carrier;
A method of manufacturing an electronic device comprising disposing an electronic-device component on a sheet,
The surface energy is 50mJ/m2 to 1000mJ/m2,
The sheet comprises glass, ceramic, or glass-ceramic,
The surface modification layer includes a plasma polymerized fluoropolymer or aromatic silane, and has a thickness of 0.1 to 100 nm,
When the electronic-device component is placed on a sheet, it is arranged to be laminated in the order of carrier, surface modification layer, sheet, and electronic-device component. Carrier with a carrier bonding surface,
Sheet with sheet bonding surface,
A surface modification layer disposed on one of the carrier bonding surface and the sheet bonding surface
A glass article comprising:
The carrier bonding surface and the sheet bonding surface are bonded with a surface modification layer between them, where the surface energy for bonding the sheet to the carrier is circulated from room temperature to 600°C at a rate of 9.2°C/min, and a temperature of 600°C After 10 minutes at, and then applying the temperature circulation to the article by heating the article in a chamber cooled to 300 DEG C. at 1 DEG C/minute, and then removing the article from the chamber and allowing the article to cool to room temperature, the carrier and If the sheet is retained and the other is not separated from each other when subjected to gravitational force, there is no outgassing from the surface modification layer during the temperature cycling, and the sheet is carriered without breaking the carrier and the thinner of the sheet into two or more fragments Having characteristics that enable it to be separated from
Obtaining glass articles;
A method of manufacturing an electronic device, comprising disposing an electronic-device component on a sheet,
The surface energy is 50mJ/m2 to 1000mJ/m2,
The sheet comprises glass, ceramic, or glass-ceramic,
The surface modification layer includes a plasma polymerized fluoropolymer or aromatic silane, and has a thickness of 0.1 to 100 nm,
When the electronic-device component is placed on a sheet, it is arranged to be laminated in the order of carrier, surface modification layer, sheet, and electronic-device component. The method of claim 1 or 2, wherein the electronic device component comprises an organic light emitting material. The method of claim 1 or 2, wherein processing the electronic device comprises processing at a temperature of ≥ 400°C. The method of claim 1 or 2, further comprising dicing the carrier and sheet into two separate parts. 6. The method of claim 5, wherein at least one of the discrete portions comprises a sheet portion that remains coupled to the carrier portion. 7. The method of claim 6, further comprising further processing at least one of the separate parts with an additional electronic-device component. 3. The method of claim 1 or 2, further comprising removing at least a portion of the sheet from the carrier, wherein at least a portion of the sheet comprises electronic device components thereon. The method according to claim 1 or 2, wherein the sheet has a thickness of ≦300 micrometers. delete delete delete delete delete delete delete delete delete delete delete

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